Extraction of several lanthanide and actinide radionuclides with crown ethers

The solvent extraction of several lanthanide radionuclides (¹⁴⁴Ce,¹⁴⁷Nd,¹⁵⁴Eu,¹⁷⁰Tm and¹⁶⁹Yb from aqueous picric acid solutions with (4-methylbenzo-15-crown-5) in chloroform has been investigated. The extracted species are found to be 1∶2∶3 (metal/crown/ picrate) complexes from slope analysis. The extraction equilibrium constants (K_ex) have been determined at 25 °C. The order of K_ex values for trivalent lanthanides is Nd³⁺> >Eu³⁺>Ce³⁺>Tm³⁺>Yb³⁺. This suggests that the ionic size of Nd³⁺ (r=0.995 Å) may be nearer to the cavity size of (4-methylbenzo-15-crown-5) than the other lanthanides. The extraction of thorium(IV) and uranium(IV, VI) by some crown ethers from nitric, hydrochloric and picric acid solutins have been studied. In nitric acid media, thorium(IV) forms a 1∶2 complex with DC18C6 or DC24C8, resembling plutonium(IV) and neptunium(IV) (identification of these reagents is given in Table 1 and Fig. 1). In hydrochloric acid media, the extraction of uranium(IV, VI) leads to a large loading and may be suitable for practical application. The far infrared spectra of the extracted complex in 1,2-dichloroethane have been examined for the UO₂Cl₂?DCI8C6, UO₂Cl₂?DC24C8, Th(NO₃)₄?DC18C6 and Th (NO₃)₄?DC24C8 systems. The spectra show the existence of direct bonding between the extracted metal ion and the oxygen donor in the ring of these crown ethers.